111772-04-4Relevant articles and documents
Decarbonylative Suzuki-Miyaura Cross-Coupling of Aroyl Chlorides
Zhou, Tongliang,Xie, Pei-Pei,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
, p. 6434 - 6440 (2020)
Herein, we report a catalyst system for Pd-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of aroyl chlorides with boronic acids to furnish biaryls. This strategy is suitable for a broad range of common aroyl chlorides and boronic acids. The synthetic utility is highlighted in the direct late-stage functionalization of pharmaceuticals and natural products capitalizing on the presence of carboxylic acid moiety. Extensive mechanistic and DFT studies provide key insight into the reaction mechanism and high decarbonylative cross-coupling selectivity.
The NMR study of the mechanism of alkene arylation with anhydrides of aromatic acids
Shmidt,Smirnov
, p. 195 - 198 (2002)
The main steps of the catalytic cycle of the alkene arylation reaction with the participation of anhydrides of aromatic acids as arylation agents were studied by 31P NMR spectroscopy. The catalytic cycle of the reaction included the steps of ox
Synthesis, Characterization, and Reactivity of α-Ketoacyl Complexes of Platinum(II) and Palladium(II). Crystal Structures of trans-Pt(PPh3)2(Cl)(COCOPh) and cis-Pt(PPh3)2(COPh)(COOMe)
Sen, Ayusman,Chen, Jwu-Ting,Vetter, William M.,Whittle, Robert R.
, p. 148 - 156 (1987)
The α-ketoacyl chloro complexes, trans-M(PPh3)2(Cl)(COCOR) (M = Pt; R = Ph, 1a; R = p-FC6H4, 1b; R = p-ClC6H4, 1c; R = p-MeC6H4, 1d; R = Me, 1e.M = Pd: R = Ph, 2), were synthesized by the oxidative addition of the appropriate α-ketoacyl chloride with either Pt(PPh3)4 or Pd(PPh3)4.The crystal structure of 1a showed a square-planar geometry around the Pt with the carbonyl groups virtually coplanar and in an s-trans configuration.The above compounds were found to decompose thermally to the corresponding benzoyl compounds, trans-M(PPh3)2(Cl)(COR).A detailed kinetic study of the decarbonylation of 1a and 2 indicated the presence of two competing pathways, one of which involved the initial dissociation of a PPh3 ligand.The kinetic and thermodynamic parameters for the various steps in the mechanism were determined.For the decarbonylation of compounds 1a-d, a correlation was observed between the rate constant for the phosphine-independent pathway and ?para.The cationic α-ketoacyl complexes, trans-Pt(PPh3)2(L)(COCOR)+BF4- (R = Ph; L = CH3CN, 4a; L = CO, 4b; L = PPh3, 4c.R = Me; L = CH3CN, 4d), were prepared by Cl- abstraction from the corresponding neutral compounds in the presence of an appropriate ligand.In the absence of any added ligand, the Cl- abstraction from 1a resulted in rapid deinsertion of CO to form cis-Pt(PPh3)2(CO)(COPh)+ (5a) initially, which then slowly converted to the corresponding trans compound, 5b.The decarbonylation of 1a to the corresponding chloro benzoyl compound was catalyzed by the addition of 5b.The addition of OMe- to 5a and 5b resulted in the formation of the acyl-alkoxycarbonyl complexes cis- and trans-Pt(PPh3)2(COPh)(COOMe), 6a and 6b, respectively.Similarly, trans-Pt(PPh3)2(COCOPh)(COOMe) (6d) was formed by the reaction of OMe- with 4b.The crystal structure of 6a revealed a square-planar geometry around the Pt with the CoPh and COOMe groups lying in planes perpendicular to the plane of the molecule.
Insertion of olefins into palladium(II)-acyl bonds. Mechanistic and structural studies
Brumbaugh, Jeffrey S.,Whittle, Robert R.,Parvez, Masood,Sen, Ayusman
, p. 1735 - 1747 (2008/10/08)
The reaction of norbornylene with [Pd(PPh3)2(CH3CN)(COR)]BF4 (2) produced [Pd(PPh3)2-(C7H10COR)](BF 4) (3). The crystal structure of 3a (R = Me) revealed a square-planar coordination around the palladium atom. The two triphenylphosphine ligands occupied cis positions, and the 2-acetylnorborn-1-yl residue acted as a chelating ligand by coordinating through the norbornyl carbon and the carbonyl oxygen. The two palladium-phosphorus distances, 2.238 (2) and 2.434 (2) ?, were dramatically different. Crystallographic data: space group P21/n; a = 11.430 (10), b = 23.042 (3), c = 16.338 (3) ?; β = 99.90 (2)°; V = 4238.7 ?3; Z = 4; R = 0.0673, Rw = 0.0894. The reaction mechanism, determined by studying the analogous reaction of 2 with norbomadiene, involved insertion from a four-coordinate intermediate formed by olefin displacement of the acetonitrile ligand. The reaction of Pd(PPh3)2(Cl)(COR) (1) with norbomylene produced Pd(PPh3)(Cl)(C7H10COR) (6). For this reaction a mechanism involving insertion from a four-coordinate intermediate formed by olefin displacement of a triphenylphosphine ligand was consistent with the experimental results. The reaction of 1 with olefin was significantly accelerated in the presence of a "phosphine sponge" (e.g., Pd(PhCN)2Cl2, CH3I, or S).
